Condensation products from an aminotriazine and trimethylolacetaldehyde



parisonEtc-formaldehyde condensation prddu; s1

Patented July 15, 1952 "t -GONlSliN SATIONi YRODUCTS' FROM AN,

/ AMINOTRIAZINE AND TRIMETHYLOD' CET LDE DE;

Main-Fechenheim'g'Ger-maiiy, assignois tosella Farbwerke Mainkur-,'-Fra1 ikfort" Main-Fechenheim, Germany- I if f i No Drawing; Application December 27, 1950,81! j v rial N l-203,009 1;!fGermanyiJanuaryflll; I (CI. 260 -675) H new jroducts contain as the "aldehyde --compb;+

rintj'ari aliphatic-aldehyde containing methylol grii'ps v hefi'presence" of these methylol-'g'rou'ps fnew' properties -o f 3 the condensation; products containing such aldehydes,"especially'ja higher solubility in water ofthejprimary coni densation products f'and a relatively high elas ticityf of the final condensation products in com-v dfithe same degree off condensation: Fur-th more these conden ation products show the v n aeeftbat t give sc c lyanytic aldeki hyde; According to these properties*'their' an? plicati'on" 'in*the industry 'produces new effects: I w en; applied in the textile industry the textile materials treated therewith exhibit 'a' remarkable; crease resistance; papers treated therewith are very pliable; lacquerse are. distinguished by their high elasticity; casting resins prepared therefrom show allow degreefof inner tension occurring v dur-- in fl lelcasting processi f X5 J S aldeh de 1 m n nts iiusedf i r the new jeonden'sation products may benamedg; tr hylolace'taldehyde,' dimethylolpropionaldemethylolisobu'tyraldehyde..7. Suitable amine compoinentsgareig urea, thi'oure'a," dicyandiamide guanidi'neffaminotriazines; and their substitution prdd ,Q'Q aminodiazines, amino-quinazolines guan lesandsoon. 7 lThe condenjsation may be carried"out vvith; r nnim le r mru v ne QmPQr n'e advantageously the presence-oi watery The 'H valueduring the'reaction'may be :above 8,, this" mariner addition compounds soluble innate: are obtainedjforming more orless distinctjcrystals. The stability of the products may furthenbeenhancedby the addition of small amountslfoflorganic bases during or after the condensation. By further heating or by a variation pfi'the'pH value to below 7 the condensa-; tioii'may be effecteduntil the formation of prod-.- ucts of limited solubility in water. This step of condensationjmay be maintained bycooling' or a by a change 'of the pH valueto above 8. ,When; these products more or less soluble inwater' are Karl x ne'r'a'iia OttdHanSen;'Franliforteon the H easily soluble inwater aresui t'able'to makfe ite tile fabrics crease-resistant orto improvethew t fiilatria solubility in water and the" products insolj water and" therefore" applicable Cas n-tll" eth rifled by means'of monovalent or polyvalent alcohols, ether-res ns are obtaiiiedf whichare mostly "insoluble in water; but" soluble "in organic solvents. To thesecompoundspolyester resins especially alkydal'e's' may 'b'e cofcohd ed before removing the vvholeamount of the -c densationwateng "a 'ufla c o ia in de o make; heififi arodff lists s ede.- lfj nds-# u p o u e. According-to the f'properties or the, condensation productsthey may b'e'used f forthe'f ollqwin j pbs iij .1 h. The solutions {of they-condensation products;

m e na ing v $5 re oi sat-i. r'ics' with solutions of the nevv condensationprod-1 uct's' w t f djd t l r' l e amount QIF ganic acids; "The products of 'a smallf degree in the 'fo ernulsions' may be used f i.'for t he manufac u're" oiiwaterxip b f en s-ld' he e a n em tu i'on jot i'thepp e a tiqns is. notriece saryq' 11 h s the ec ns qn l t'sji i e y: distinguished 'frorn'th'e known methods, jb QQ a,

according to theklatt'er methods melamine f rni aldehyde" ccnde nsatiorr productsare 'suitable "tor the; said pu ipqsef only after ifconverting their aqueou s 'solutions"into ahigher degree offlc densation'by the addition offlarge amb r; strong acids."- The fact-that in 'such a casela amonntsofa'cids are to be added is known to- 'b e undesirable for the paper makerj" In contradis tinction" hereto the new' process using the can-g densati'on products of this invention-is mueh simpler." It shows the following' advantage good solubilit y of the used products "without the 'iie'ed oiia specialheating; avoiding the' additidnof an acid and troubles because of bad-smell; use of the solutions immediately after 1 the dilution 0f. the products, no further heating operation" for readymad'epaper..-.;=-- :.l. i The products-insoluble in wat'er and' the fore useful in the form of emulsions may be used as 's'tovln'gl lacquers which forr'nt.when heated to about- 3120? white films of: a goodi elasti'cityi and a high .brilliancy: :;:.The; co =c'ondensation prod-f' ucts 'Qf the partially; etherified Lc'ofndens'ation products and polyester tresinsmayube'i also used as lacquer resins; Furthermore'the'seprodhotsmay 5 5 begused: as casting resinsand'yield.wherr-nsed-as time: these condensation pri dff I a tion but are not intended to limit it thereto; the parts'are givenby weight and all t I in centigrade degrees.

' ii'era q d o b and n for S ver l h u r re addedto the imp 1 this product (correspondingto 20.41 g. anaemi- 3 r such milkwhite or colorlesstransparent' masses of a strong refraction of light, showing a good hardness and stability and no cracks when stored foralongertime. v The following examples illustrate the' invene emperatures I I Example 1' r p 63 parts of melamine are mixed with 160 parts of a concentrated 83.5% solution of. trimethylol acetaldehyde (prepared. from acetaldehyde "and formaldehyde with sodium carbonate. 1 as; .a-'ca H alyst) with .the addition'of 80 parts of water. Then caustic soda solution is added until the 7 mixture shows an alkalme"reaction. The'mass; f

is stirred and heated gradually-W802 During this operation the alkalinity is maintainedif necessary during the process by means of small amou te cpncen ra edsqd umca b a so io :The sq u cn. h s b a n d. ,is n a tl cooled. I Thereby 305 partsof a viscous solution are; obtained Whichbecome pasty when there-.

onsolidifiedin a form of a paste of fine crystals. The product contains about 4.5% of an addi- .Q u tpf 2. mo t i eih iqlaeetal ehy n 1 9. mine.) I iw e r edlublein m llm n s wa wa h menace so filutiorrmayfbadiluted further by means ofcold water'. A product still: better. storable but et erwise showing nearly the same 'qualitieslis ob; iai awwnen the foregoing mixture '14." parts of triethanolamine are added before heatingito 802. A furtheraddition of the sodium carbon .in

l l e 'bs- 6f e i e fi l thus! bam' di qrresp'o'riding tol about 18.5 parts of a; -100% product. which 'nia'yf or" may not j. contain Yethan'olamine,

' arf dissolved 3.0 partsof warm water, at a temperature of about 40"; This solution is made up by means or water" to' L ltr. Viscosefr'ayon fabriciis. impregnated with this solution 'forisey er'alm'inutes,.squeezedand dried. After 1.01m ute's heating 110 the fabricshows a remarkable riseot the, crease resistance when. cormiared'with i the. untreatediabricila further rise'is by..l'ieatingto 130 tor'lflminutes. .,Wheu;4lccm. per liter of a"35.7%' g'lycoliofacid tinsl s lu n 5 rs th it ia r iseb e ne J t 1 T 1W l b i an m r v e owns l E- in= 2Wise Q h wet t n h "spawn 5 s u qnp m ofl-trih dro;iyn ethylt-fa hydroxyethyli-melamine rere, ingtheflfabricwi 3 are 3 917 1171 mole melamine nd 1 mole-brie methylolace 1 m qnziabriqar sefof th Y 1 ready. by Iafterheatingj the fabric. to 110.T31he c mpflundmrepared from-'1 molemelamine and i 6,, molestrimethylolacetaldehyde 1is obtained par:

:tially'as starelikeicrystal needles. The N-co'n-i- I tent of the'jdried crystallizediproduct is".9:23%r whereas the theoretical N-contentzof hexa;

ialdehydei p p esdo the: same crease resistance; .al-,

us trihydroxymethyl-a-hydroxyaethyl).emelaminei is :When per 'liter of the Solution Of tcn'free: product) isappliedl onto. the. fabricwithoutthe. addition of an acid 'catalyst asimilar V efiect'is produced by 1U minuteslafterheating ot the'fabric 120110 or 130 I By means'cof. 31 g. perliter oft-'17 solution a d o v moreFstable' products are obtained.

' shows a-r'markable crease resistan '4' V of a condensation product of lower molecula Weight which is prepared in an analogous Way by starting from 1 mole urea and 1 mole tri- 1 methylolacetaldehyde a remarkablezcrease resistanceis'produced. By treatin athe fabric in this solution containing furthermore 4 g. 'per liter of .glycolic acid an improvementof the wet strength is simultaneously produced.

. By a subsequent. addition of small amounts of orgargicbases {if} i. pyridine,.piperidine, ethanolamines and soon) to the newly prepared concenlutions-of the products herein described;

J 62.6 parts of acetogu'anamine are mixed with 30f116" parts{off ;a j88% solution of trimethylolacetaldehyde and 75 parts of water. The mixl ture'xis rendered ,Weakly alkaline by means of caustic soda solution audit is heated while stirring to w 79?. V The clear solution thusiormiemis further heated for 1 hour to 80. rqc he k li ity i .maintained' y-. h :xaddiv 9 sodium a bo at 1112 0 4 A t r cool-i eii oart q -ayi c c a olut n. of: 356 %i of the n s ti up od ct o mo e cetoe a'n: amine, and 4- moles; ttimethylolacetal dehyde is; obtained. i The;yiscous,' solutionpi this compound isclear dilutable; with any-. amount .o f;fwater By eedi or lon ime si plutio o m ns e or? cr sta ase qm ed In; .e et h r u t when s ed i t-about. thefsame quantity of lukewarm water is, 1ilge 1, 7 Wise lu abl wit t -em 0f i diiwet a thi The. product represents probably a mixture q f niolecularly ethlerified compound. .4 2-

' h t mel om o n amen, mite-I liter .of -.water. ;at room temperature. Atter the.

advantageously at sogioi [then squeezed, (in u;- at v' 70 80""ai'i d aftercondensed for 10minutes; at. 113". In this waya fabric obtained which bility'int lwetandidrystate.

Example-:3

$311 p i i'of' ml or a @1165: arts 513613.95. trimethylolacetaldehyde, b stirring a iemeauiig" T fiii h sQIu im mad n t a- H'r h e-o meansof caustic "soda solution andfiiiain tame at a-temperature of "80: for. 30 .1 'Qmi i until atest be mass is instantly cooled toroom tempe H ningaboutj"68%joff'the condelisaI-l tion product V p v obtained. oduct'ithu prepare N re; d by means of toluen' o e .qe oi l'*so i nith s obtained is addedto a pa'perpulp consisting f degree of 1 hydration. y w en thefmass. is; wen

e per square meter jweight. 1

rriseaper thus iireisaied isdistinguished ht ur n .t is

r V i ey nv ebde is impregnated forashorttimeinthis-solution I amine are' dissolvedin-a'miii- .t'ureof 440 parts of wat a high degree df Wet strength-"without needing a y separate erir imemat e va t pe ature. When it is further treated" with a small amount of resin glue (1% calculated for colophonium is sufficient) a good sizing efiect is obtained besides the said improvement of the wet strength.

' 63 parts of melamine aremi ed with 140. parts of water and 401 parts of a concentrated solution (83.5%) of trimethylolacetaldehyde. The neutral mixture is heated to 70 as fast as possible without an addition of alkali, whereby dissolution occurs. Then a solution of caustic soda and finally a concentrated sodium carbonate solution are added, so that the solution clearly shows an alkaline reaction. Thereupon a temperature of 80 is maintained for about 30 minutes, whereafter it is immediately cooled down. About 600 parts are obtained of a solution which is viscous at room temperature and shows a somewhat higher degree of viscosity and a slight opalescence after standing some time; the solution contains about 65% of the condensation product thus formed.

When paper is treated with this product in a process as outlined in Example 3, a paper of improved wet-strength is obtained,

Example 84 parts of dicyandiamide and 223 parts of 86.3% trimethylol-acetaldehyde are dissolved at 70-80 by adding '70 parts of water. This solution is then condensed during 1% hours at about 95, a slight alkalinity being maintained by adding small amounts of sodium carbonate solution. Thereupon about 70 parts of water are distilled 011 during about 50 minutes at 95, on stirring in an air-stream. Then distilling is discontinued but stirring is continued at 95 until a test made with a small part of the viscous product obtained shows turbidity when diluted with more than 3 parts of water. About 317 parts of a highly viscous condensation product are obtained, containing 1 mole dicyandiamide and 1 moles trimethylolacetaldehyde.

With this product a paper of high wet strength can be produced in a similar manner as indicated in Example 3, when 4-5 parts of the product, dissolved in water, are added to a paper pulp of 100 parts of cellulose. The application of this condensation product offers the advantage that it may be embodied into the paper pulp when dissolved in water only, without necessitating the use of alcohol.

Example 6 315 parts of melamine are stirred with 2310 parts of 86.5% trimethylolacetaldehyde and 800 parts of water. Then, after rendering the mixture slightly alkaline, 3400 parts of butanol are added. The distillation receiver is filled with toluene, heating is started, and the mixture is distilled azeotropically until about '700 parts of water are distilled oil. The butanol-toluenemixture is returned to the reaction receptacle.

Then 10 parts of phthalic anhydride, dissolved in some butanol, are added. Azeotropical distillation is continued until a, total of about 1400 parts of the aqueous solution is distilled off. The duration of the distillation is in total 4 hours, during which the inner temperature of the lacquer-solutions rises to about 118. .About 5350 parts of raw lacquer are obtained from which impurities (f. 1. small amounts of salt set free,

' forms-awithout addition of .anialkydqresin 8.1-!-

ready-a. white film having a'very, good elasticity as .well as'igood. hardness when stoved at 120. In case before 'j spraying there is mixed to the lacquer besides a pigment an alkyd resin (1?. i. the one known on the market as Alkydal RD 18 or Alkydal T) at the rate of 3:7, films are obtained from this mixture which, stoved at 120, are of an extremely improved elasticity and of very good hardness. Even when stoved at 180 this elasticity is impaired little, while a higher degree of hardness is obtained.

In case the condensation as described above is performed with about 1 part of 10 n-hydrochloric acid instead of using the phthalic acid catalyst (condensation temperature rising up to 120 and a little more of condensation water distilling off) a lacquer resin is obtained which, when mixed with an alkyd resin, produces films of a good elasticity and high brilliancy.

In case the etherification is performed with benzyl alcohol instead of n-butanol with a temperature-limit at 170 on condensation, a lacquer resin is produced from which (even without an incorporation of an alkyd resin; stoved at 120) films with an exceedingly high brilliancy and very good elasticity are obtained. When condensing up to a temperature of 141 only, the lacquer resin obtained (especially in mixture with a modified alkyd resin prepared from phthalic anhydride, glycerol and linseed oil) results in films which, when stoved at 120 as well as at 180, possess a very good brilliancy and a very high degree of elasticity, when stoved at 180 also a very good hardness is obtained.

Example 7 31.5 parts of melamine are dissolved in a solution of 192.5 parts of 86.5% trimethylolacetaldehyde in parts of water by heating to 80. Then 444 parts of butanol are added. This mixture undergoes an azeotropical distillation until 65 parts of water are distilled oil. 1 part of phthalic anhydride is added and-while stirring at the same time-distillation is continued until parts of water are distilled off. Thereupon are added 148 parts of a solution (containing 37.2% cyclohexanone and butanol) of a polyester prepared from 3 molecular proportions of pentaerythrite and 4 molecular proprotions of adipic acid (polyesterified finally in presence of cyclohexanone and butanol up to an acid number of 134). The cocondensation is executed on distilling further azeotropically until an inner temperature of 117 is reached and a total of 148 parts of water is distilled oif. About 530 parts of a 50% solution of the mixed condensation product are obtained. This lacquer resin produces, when stoved at 120, white films of a medium silky brilliancy, having good hardness and outstanding elasticity.

We claim:

1. As new compounds the condensation products of melamine and trimethylolacetaldehyde among which compounds the representatives of a lower degree of condensation show a high solubility in water and the representatives of a higher degree of condensation a high elasticity.

2. As new compounds the condensation products of an aminotriazine and trimethylolacetaldehydeeamong' .whichcompounds the riepresen- REFERENCESQCITED.

. tativfis lower degree Ofcondensafionshow "The foilowihrefreh"are of record 'in the highsolubility in water and the representatives p g r of a higherdegree 01' condensation ahighwelas-i V :V- ticity. v 5 v f UNITED STATES PATENTS J -3. Process which comprises condensingv' an r I aminotl iazine with trimethylolagetaldehydein" 32 g f gfg the presence of an alkali and of water. 2320820 Ema-id Jun; 1943 i KELLER 2,369,948 -DA1e1io: Feb. :20, 1945 OTTO HANSEN. 10 V r I 7 

2. AS A NEW COMPOUNDS THE CONDENSATION PRODUCTS OF AN AMINOTRIAZINE AND TRIMETHYLOLACETALDEHYDE AMONG WHICH COMPOUNDS THE REPRESENTATIVES OF A LOWER DEGREE OF CONDENSATION SHOW A HIGH SOLUBILITY IN WATER AND THE REPRESENTATIVES OF A HIGHER DEGREE OF CONDENSATION A HIGH ELASTICITY. 